1. Field of the Invention
The present invention relates to a refrigerant mixture which is useful as a substitute for chlorodifluoromethane (CHClF2, HCFC-22). More particularly, the present invention relates to a refrigerant composition which is useful as a substitute for HCFC-22, which comprises a first constituent of difluoromethane (CH2F2, HFC-32); a second constituent of pentafluoroethane (CHF2CF3, HFC-125); a third constituent of 1,1,1-trifluoroethane (CH3CF3, HFC-143a); a fourth constituent selected from the group consisting of cyclopropane (C3H6, RC-270), 1,1,1,2,3,3,3-heptafluoropropane (CF3CHFCF3, HFC-227ea), 1,1,1,2,2-pentafluoropropane (CH3CF2CF3, HFC-245cb), isobutane (CH(CH3)2CH3, R-600a), octafluorocyclobutane (C4F8, RC-318), 1,1,1,2,3,3-hexafluoropropane (CHF2CHFCF3, HFC-236ea), butane (C4H10, R-600), bis(difluoromethyl)ether (CHF2OCHF2, HFE-134) and pentafluoroethylmethylether (CF3CF2OCH3, HFE-245).
2. Description of the Background Art
As is well known, CFC compounds have been restricted in production and use in accordance with the Montreal Protocol because they have been found as a main factor in contributing to the destruction of the ozone layer. In advanced nations, the use of such CFC compounds has already been banned since 1996. It is also known that HCFC-based compounds such as HCFC-22 have considerable effects in causing damage to the ozone layer even though this effect is less severe than those of the CFC compounds. For this reason, a restriction has been made to gradually reduce the use of such HCFC-based compounds. A plan has also been made to ban the use of HCFC-based compounds about the year 2020.
This has resulted in a number of world-wide research efforts to produce substitute materials coping with the restriction in use of HCFC-22 which will be more severe in the future. The representative examples of a substitute refrigerant mixtures are HFC-407C and HFC-410A proposed by the American Society of Heating. Refrigerating and Air-Conditioning Engineers (ASHRAE). HFC-407C is a refrigerant mixture of HFC-32/125/134a in a ratio of 23/25/52 (based on weight percent). Meanwhile, HFC-410A is a refrigerant mixture of HFC-32/125 in a ratio of 50/50 (based on weight percent).
In addition, U.S. Pat. No. 5,080,823 discloses a mixed refrigerant composition of HFC-143a/opropane (C3H8), U.S. Pat. No. 5,185,094: HFC-32/125/134a, U.S. Pat. No. 5,211,867: HFC-125/143a, U.S. Pat. No. 5,234,613: HFC-32/propane, U.S. Pat. No. 5,236,611: PFC-218/HFC-143a, U.S. Pat. No. 5,290,466: HFC-32/134a/134, U.S. Pat. No. 5,340,490: HFC-23/CO2 or HFC-23/116/CO2, U.S. Pat. No. 5,403,504: HFC-125/32, U.S. Pat. No. 5,429,760: HFC-23/134a, U.S. Pat. No. 5,538,660: HFC-32/HFC-134a/FC-14 or HFC-32/HFC-134a/PFC-218, and U.S. Pat. No. 5,643,492: HFC-32/125/134a.
Also, Japanese Patent Laid-open Publication No. 172386/1991 discloses a mixed refrigerant composition of HFC-32/125/152, Japanese Patent Laid-open Publication No. 170594/1991: HFC-23/125/134a, Japanese Patent Laid-open Publication No. 170592/1991: HFC-32/143a/152a, Japanese PatentLaid-open Publication No. 170593/1991: HFC-23/125/32, Japanese Patent Laid-open Publication No. 170591/1991: HFC-23/143a/134a, Japanese Patent Laid-open Publication No. 170590/1991: HFC-125/134a/32, Japanese Patent Laid-open Publication No. 170589/1991: HFC-23/143a4152a, Japanese Patent Laid-open Publication No. 170588/1991: HFC-125/143a/134a, Japanese Patent Laid-open Publication No. 170587/1991: HFC-32/134a/152a, Japanese Patent Laid-open Publication No. 170586/1991: HFC-32/143a/134a, Japanese Patent Laid-open Publication No. 170585/1991: HFC-32/125/134a, Japanese Patent Laid-open Publication No. 170584/1991: HFC-23/134a/152a, Japanese Patent Laid-open Publication No. 170583/1991: HFC-125/143al32, Japanese Patent Laid-open Publication No. 222893/1992: HFC-32/125, Japanese Patent Laid-open Publication No. 154887/1992: HFC-134/152a, Japanese Patent Laid-open Publication No. 117645/1993: HFC-23/134a/propane, Japanese Patent Laid-open Publication No. 117643/1993: HFC-125/134a/propane, Japanese Patent Laid-open Publication No. 65561/1994: HFC-23/152a/PFC-218, Japanese Patent Laid-Open Publication No. 128872/1994: HFC-32/PFC-218, Japanese Patent Laid-Open Publication No. 220433/1994: HFC-32/125/RC-318, Japanese Patent Laid-Open Publication No. 173462/1995: HFC-143a/125/134a/heptane (C7H16), Japanese Patent Laid-open Publication No. 176537/1996: PFC-218/RC-270/HFC-152a, Japanese Patent Laid-open Publication No. 151569/1996: propane/RC-270/HFC-34a, Japanese Patent Laid-open Publication No. 127767/1996: HFC-32/134a/RC-318, Japanese Patent Laid-open Publication No. 25480/1997: HFC-32/134a/125/isobutane, Japanese Patent Laid-open Publication No. 59611/1997: HFC-134a/isobutane, Japanese Patent Laid-Open Publication No. 208941/1997: HFC-32/152a/125/RC-270, and Japanese Patent Laid-open Publication No. 221664/1997: HFC-125/143a/134a/RC-270.
Also, Korean Patent Publication No. 93-10514 (Application No. 90-19594) discloses a mixed refrigerant composition of HFC-23/132/152a, HFC-23/125/152a, HFC-32/143a/152a, HFC-125/143a/152a, HFC-32/125/125a, HFC-23/143a/152a, or HFC-23/125/152a, Korean Patent Publication No. 93-10515 (Application No. 90-19596): HFC-23/32/134, HFC-23/32/134a, HFC-23/125/134a, HFC-23/125/134, HFC-32/125/134, HFC-23/143a/134a, HFC-32/125/134a, HFC-125/143a/134a, or HFC-125/143a/134, Korean Patent Laid-Open Publication No. 96-4485 (Application No. 95-21221): HFC-32/23/134a, Korean patent Laid-open Publication No. 95-704438 (Application No. 95-701865): HFC-32/125/134a, Korean patent Laid-open Publication No. 96-701168 (Application No. 95-704038): HFC-227ea/HFC-152a, and Korean Patent Laid-open Publication No. 97-704853 (Application No. 97-700436): HFC-134a/HCFC-124/butane.
Therefore, an object of the present invention is to provide a novel refrigerant mixture which is useful as a substitute for HCFC-22. That is, the present invention has an object to provide a refrigerant composition produced by mixing additionally one component of RC-270, HFC-227ea, HFC-245cb, R-600a, RC-318, HFC-236ea, R-600, HFE-134 and HFE-245 with a mixture of HFC-32, HFC-125 and HFC-143a, thereby producing a composition capable of exhibiting properties similar to HCFC-22.
The present invention relates to a refrigerant composition which is useful as a substitute for HCFC-22, which comprises a first constituent of difluoromethane (CH2F2, HFC-32); a second constituent of pentafluoroethane (CHF2CF3, HFC-125); a third constituent of 1,1,1-trifluoroethane (CH3CF3, HFC-143a); a fourth constituent selected from the group consisting of cyclopropane (C3H6, RC-270), 1,1,1,2,3,3,3-heptafluoropropane (CF3CHFCF3, HFC-227ea), 1,1,1,2,2-pentafluoropropane (CH3CF2CF3, HFC-245cb), isobutane (CH(CH3)2CH3, R-600a), octafluorocyclobutane (C4F8, RC-318), 1,1,1,2,3,3-hexafluoropropane (CHF2CHFCF3, HFC-236ea), butane (C4H10, R-600), bis(difluoromethyl)ether (CHF2OCHF2, HFE-134) and pentafluoroethylmethylether (CF3CF2OCH3, HFE-245).
It is preferred that the refrigerant composition of the present invention comprises a first constituent of 15 to 95% by weight difluoromethane (CH2F2, HFC-32); a second constituent of an amount up to 60% by weight pentafluoroethane (CHF2CF3, HFC-125); a third constituent of an amount up to 70% by weight 1,1,1-trifluoroethane (CH3CF3, HFC-143a); a fourth constituent of an amount up to 50% by weight comprising one selected from the group consisting of cyclopropane (C3H6, RC-270), 1,1,1,2,3,3,3-heptafluoropropane (CF3CHFCF3, HFC-227ea), 1,1,1,2,2-pentafluoropropane (CH3CF2CF3, HFC-245cb), isobutane (CH(CH3)2CH3, R-600a), octafluorocyclobutane (C4F8, RC-318), 1,1,1,2,3,3-hexafluoropropane (CHF2CHFCF3, HFC-236ea), butane (C4H10, R-600), bis(difluoromethyl)ether (CHF2OCHF2, HFE-134) and pentafluoroethylmethylether (CF3CF2OCH3, HFE-245).
In accordance with the present invention, the refrigerant composition as mentioned above is applied to a refrigeration system which comprises a compressor, a condenser, an expansion valve, and an evaporator in order to evaluate the coefficient of performance (COP), the volumetric capacity of refrigerant (VC), and pressures in the compressor and evaporator. The novel refrigerant mixture according to the present invention is evaluated to be substantially equivalent to HFC-407C or HFC-410A in terms of performance. Accordingly, the refrigerant mixture of the present invention is useful as a substitute for HCFC-22.
Where the refrigerant composition of the present invention includes HFC-32, HFC-125, HFC-143a and RC-270, the composition comprises 15 to 60% by weight of HFC-32, an amount up to 50% by weight of HFC-125, 20 to 70% by weight of HFC-143a and an amount up to 15% by weight of RC-270, and preferably, the composition comprises 25 to 45% by weight of HFC-32, 2 to 35% by weight of HFC-125, 28 to 60% by weight of HFC-143a and an amount up to 10% by weight of RC-270.
Where the refrigerant composition of the present invention includes HFC-32, HFC-125, HFC-143a and HFC-227a, the composition comprises 20 to 60% by weight of HFC-32, an amount up to 60% by.weight of HFC-125, an amount up to 70% by weight of HFC-143a and an amount up to 50% by weight of HFC-227a, and preferably, the composition comprises 28 to 50% by weight of HFC-32, 2 to 50% by weight of HFC-125, 5 to 60% by weight of HFC-143a and an amount up to 40% by weight of HFC-227ea.
Where the refrigerant composition of the present invention includes HFC-32, HFC-125, HFC-143a and HFC-245cb, the composition comprises 20 to 90% by weight of HFC-32, an amount up to 60% by weight of HFC-125, an amount up to 60% by weight of HFC-143a and an amount up to 50% by weight of HFC-245cb and preferably, the composition comprises 30 to 85% by weight of HFC-32, 2 to 45% by weight of HFC-125, 3 to 50% by weight of HFC-143a and an amount up to 40% by weight of HFC-245cb.
Where the refrigerant composition of the present invention includes HFC-32, HFC-125, HFC-143a and R-600a, the composition comprises 30-60% by weight of HFC-32, an amount up to 45% by weight of HFC-125, 15 to 50% by weight of HFC-143a and an amount up to 20% by weight of R-600a, and preferably, the composition comprises 38 to 50% by weight of HFC-32, 5 to 35% by weight of HFC-125, 20 to 43% by weight of HFC-143a and an amount up to 15% by weight of R-600a.
Where the refrigerant composition of the present invention includes HFC-32, HFC-125, HFC-143a and RC-318, the composition comprises 20 to 60% by weight of HFC-32, an amount up to 45% by weight of HFC-125, 10 to 50% by weight of HFC-143a and an amount up to 20% by weight of RC-318, and preferably, the composition comprises 30 to 48% by weight of HFC-32, 10 to 35% by weight of HFC-125, 20 to 40% by weight of HFC-143a and an amount up to 15% by weight of RC-318.
Where the refrigerant composition of the present invention includes HFC-32, HFC-125, HFC-143a and HFC-236ea, the composition comprises 20 to 85% by weight of HFC-32, an amount up to 40% by weight of HFC-125, an amount up to 60% by weight of HFC-143a and an amount up to 30% by weight of HFC-236ea, and preferably, the composition comprises 30 to 75% by weight of HFC-32, 5 to 30% by weight of HFC-125, 5 to 48% by weight of HFC-143a and an amount up to 20% by weight of HFC-236ea.
Where the refrigerant composition of the present invention includes HFC-32, HFC-125, HFC-143a and R-600, the composition comprises 25 to 70% by weight of HFC-32, an amount up to 60% by weight of HFC-125, an amount up to 40% by weight of HFC-143a and an amount up to 20% by weight of R-600, and preferably, the composition comprises 35 to 60% by weight of HFC-32, 5 to 50% by weight of HFC-125, 5 to 33% by weight of HFC-143a and an amount up to 12% by weight of R-600.
Where the refrigerant composition of the present invention includes HFC-32, HFC-125, HFC-143a and HFE-134, the composition comprises 30 to 95% by weight of HFC-32, an amount up to 50% by weight of HFC-125, an amount up to 40% by weight of HFC-143a and an amount up to 15% by weight of HFE-134, and preferably, the composition comprises 40 to 88% by weight of HFC-32, 2 to 40% by weight of HFC-125, 2 to 30% by weight of HFC-143a and an amount up to 10% by weight of HFE-134.
Where the refrigerant composition of the present invention includes HFC-32, HFC-125, HFC-143a and HFE-245, the composition comprises 30 to 90% by weight of HFC-32, an amount up to 50% by weight of HFC-125, an amount up to 45% by weight of HFC-143a and an amount up to 15% by weight of HFE-245, and preferably, the composition comprises 40 to 85% by weight of HFC-32, 5 to 40% by weight of HFC-125, 5 to 38% by weight of HFC-143a and an amount up to 10% by weight of HFE-245.